TW574416B - Metal film and manufacturing method therefor, and laminated ceramic electronic component and manufacturing method therefor - Google Patents
Metal film and manufacturing method therefor, and laminated ceramic electronic component and manufacturing method therefor Download PDFInfo
- Publication number
- TW574416B TW574416B TW91111046A TW91111046A TW574416B TW 574416 B TW574416 B TW 574416B TW 91111046 A TW91111046 A TW 91111046A TW 91111046 A TW91111046 A TW 91111046A TW 574416 B TW574416 B TW 574416B
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- TW
- Taiwan
- Prior art keywords
- metal film
- film
- metal
- manufacturing
- forming
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 395
- 239000002184 metal Substances 0.000 title claims description 394
- 238000004519 manufacturing process Methods 0.000 title claims description 77
- 239000000919 ceramic Substances 0.000 title claims description 62
- 239000010408 film Substances 0.000 claims description 436
- 238000000034 method Methods 0.000 claims description 68
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 31
- 238000007772 electroless plating Methods 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- 210000001161 mammalian embryo Anatomy 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000007654 immersion Methods 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000009713 electroplating Methods 0.000 claims description 6
- 230000012010 growth Effects 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims 1
- 238000005034 decoration Methods 0.000 claims 1
- 229940098465 tincture Drugs 0.000 claims 1
- 238000009941 weaving Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 description 13
- 239000003985 ceramic capacitor Substances 0.000 description 9
- 230000007547 defect Effects 0.000 description 8
- 229910001096 P alloy Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- -1 oblique Chemical compound 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- HIJDQYZZPATXAO-UHFFFAOYSA-N palladium hydrochloride Chemical compound Cl.[Pd] HIJDQYZZPATXAO-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000555745 Sciuridae Species 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 239000012771 household material Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011104 metalized film Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/20—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1605—Process or apparatus coating on selected surface areas by masking
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1657—Electroless forming, i.e. substrate removed or destroyed at the end of the process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/073—Displacement plating, substitution plating or immersion plating, e.g. for finish plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
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- Microelectronics & Electronic Packaging (AREA)
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Ceramic Capacitors (AREA)
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- Laminated Bodies (AREA)
Description
1 '發明説明（ 本發明有關金屬膜及其製造方 一 有關疊層陶替雷孑 疋件及其製造方法。特別是’本發明有關金屬膜的製造方 ❿风且適用於爲 層陶瓷電子元件内作為内部導電膜。 、丘 疊層陶瓷電子元件（例如多層陶瓷電容器）設有内部導電 膜例如内部電極。内部導電膜可藉多種方法形成。典型實 例包括：使用厚膜成形技術例如導電糊印刷及烘烤^成二 部導電膜；或使用薄膜成形技術例如真空薄膜成形^法譽 成内部導電膜，例如使用真空蒸發或濺射，或滿贵ς (例如無電鍍法或電鍍法）。 本發明有關使用後者薄膜成形技術製成内部導電膜的方 法，亦即金屬膜之製造方法。 、、 使用薄膜成形技術的金屬膜製造方法為公知，例如曰本 未審查專利申請公報6-302469揭示一種方法，其中經由掩 模藉真空薄膜成形方法在有機膜（支撐元件）上形成厚度爲 〇·1至0.3微米的第一金屬膜。藉無電鍍在第一金屬膜上形成 第二金屬膜，由此製造具有預定厚度的金屬膜。 爲了用作疊層陶瓷電子元件的内部導電膜，在有機膜上 所形成金屬膜必須滿足下述條件：有機膜須可藉一些步驟 自金屬膜剝離，例如自有機膜轉移到陶瓷生板 green sheet)上 〇 然而’日本未審查專利申請公報6-3〇2469描述之技呈 有下述問題。 ^ 當金屬膜在未發生缺陷的條件下形成時，存在的問題 574416 A71 'Explanation of the invention (The present invention relates to a metal film and a manufacturing method thereof, and to a laminated terraperide piece and a manufacturing method thereof. In particular, the present invention relates to a metal film manufacturing method and is suitable for a multilayer ceramic electronic component. The inner conductive film is used as an internal conductive film. Yau multilayer ceramic electronic components (such as multilayer ceramic capacitors) are provided with internal conductive films such as internal electrodes. The internal conductive film can be formed by a variety of methods. Typical examples include the use of thick film forming techniques such as conductive paste printing. And baking ^ to form two conductive films; or use thin film forming techniques such as vacuum thin film forming ^ to form internal conductive films, such as using vacuum evaporation or sputtering, or expensive (such as electroless plating or electroplating). The invention relates to a method for forming an internal conductive film using the latter thin film forming technology, that is, a method for manufacturing a metal film. A method for manufacturing a metal film using the thin film forming technology is well known, for example, Japanese Unexamined Patent Application Publication No. 6-302469 discloses a method A method in which a thickness of 0 · 1 is formed on an organic film (supporting member) by a vacuum thin film forming method through a mask. A first metal film of 0.3 micron. A second metal film is formed on the first metal film by electroless plating, thereby manufacturing a metal film having a predetermined thickness. For use as an internal conductive film of a laminated ceramic electronic component, on an organic film The formed metal film must meet the following conditions: the organic film must be peelable from the metal film by some steps, such as being transferred from the organic film to a ceramic green sheet). However, 'Japanese Unexamined Patent Application Publication 6-3〇2469 describes The technical presentation has the following problems. ^ Problems when metal film is formed without defects 574416 A7
金屬膜與支撐元件間之剝離，且隨後 陶竞生板上。此轉移的時間延長，部分全=法轉移到 爲…： 出現破損或裂紋等。 ’、、、解、仏問題’有效之方法為使其 屬膜之間黏合力降低。因此，已經採取措心：金 發二組合用於支撑元件的材料和用於第_金屬膜的二 些關於形成第一金屬膜的薄膜成形方法制 造條件的發明。 ’專膜:衣 ，而’當支撐s件和金屬膜之間的黏合如上所述降低 ，由於猎真空薄膜成形設備形成第一金屬 =形成第二金屬膜之無電鍛後之水洗，金屬膜内： 生應力而可能在金屬膜内發生剝離。因此，遭遇缺陷問題 ’如金屬膜中可能發生部分剝離和裂紋。 爲了克服該問題，構思了一種方法，其中爲了避免由於 金屬膜成形期間剝離引起的缺陷，在黏合力儘可能降低到 在該黏合範圍0改進脫模性的同時，確保將金屬㈣定在 支撐元件上的黏合力。爲了實現該方法，曾經提出精確控 制支#元件和金屬膜間黏合力的方法。例如，日本未審: 專利申明公報7 - 6 6 0 7 2揭示將第一金屬膜的針孔開口面積 比特定在1至70%。金屬膜能夠可靠地固定在支撐元件上， 同時控制自支撐元件剝離金屬膜之剝離力。 然而，藉此習知技術抑制金屬膜成形期間發生的剝離使 支撐元件和金屬膜間的脫模性劣化。因此，上述日本未審 查專利申請公報6 - 3 0 2 4 6 9的問題在於支撐元件和金屬膜間 本紙張尺度通用中國國家標準(CNS) Α4規招:(210 X 297公釐)The metal film was peeled from the support element, and then it was on a ceramic plate. The time for this transfer is prolonged, and some of them are transferred to the method as ...: Damage or crack appears. It is effective to reduce the adhesion between the metal membranes. Therefore, measures have been taken: the combination of the material for the support member and the metal film for the first metal film is related to the invention of the manufacturing conditions of the thin film forming method for forming the first metal film. 'Special film: clothing,' When the adhesion between the support and the metal film is reduced as described above, the first metal is formed by the hunting vacuum film forming equipment = the second metal film is washed with water after electroless forging. : Stress may cause peeling in the metal film. Therefore, a defect problem is encountered, such as partial peeling and cracks may occur in the metal film. In order to overcome this problem, a method is conceived in which, in order to avoid defects due to peeling during the formation of the metal film, the adhesion force is reduced as much as possible to improve the releasability in the adhesion range 0, while ensuring that the metal is fixed to the support member Adhesion. In order to realize this method, a method for precisely controlling the adhesion between the support element and the metal film has been proposed. For example, Japanese Unexamined Patent Publication 7-6 0 7 2 discloses that the pinhole opening area ratio of the first metal film is specified to be 1 to 70%. The metal film can be reliably fixed on the supporting member, and at the same time, the peeling force of the metal film from the self-supporting member can be controlled. However, by this conventional technique, the occurrence of peeling during the formation of the metal film is suppressed to deteriorate the releasability between the support member and the metal film. Therefore, the above-mentioned Japanese Unexamined Patent Application Gazette 6-3 0 2 4 6 9 has a problem between the supporting member and the metal film. The paper size is generally in accordance with the Chinese National Standard (CNS) A4. Regulation: (210 X 297 mm)
裝 訂Binding
線 五 、發明説明（ 的剝離，進一步說，無法轉移到陶瓷生板上， 加，。卩分金屬膜未轉移且保留在支撐元件 曰 囚此合Μ 8苢 上出現破損或裂紋等，這些問題尚未完全克服。 、 :本未審查專利中請公報7.66G72揭示_種技術，其中菜 ^第一金屬膜直到厚度約〇· i微米之等級。當，、 達到此厚度時，第一全屬膜# 游δ直到 均勾連續膜。正如上述文獻所述，較形成針孔時 例中其大小爲1微米，通常爲〇 5微米或更大。 貝匕 鋒：果，雖然在1 χ 105_2的某些區域能夠形成均勾的連 10 nm2的其他區域可能變成針孔的 :二’ t疋在1 x 10W的某些區域僅能看到針孔的-個 或兩個邊線，1 一 < ， 1 分，且可能變成在該範圍内不存在金屬膜的狀況„ -口此白知技術中，热法達到圖5所示的條件，其中金 『在1 X 10W的任何區域内為島嶼結構或網狀結構。亦 :雜ί於日本未審查專利申請公報7_66G72摇述的技術控制 ^為所謂之剝離巨觀控制。因此，當採用可展現強的脫 吴二此的條件時，i生之問題為用於第—金屬膜的金屬與 支撑-件的組合以及薄膜成形方法中臈形成條件。由於成 版過程中，或者㈣過程中或者㈣後水洗過程中，在金 :膜中針孔以外的部分内產生之内部虔力使金屬膜中可能 =裂紋且金屬膜可能剝離，因此難以形成沒有缺陷例如 邛分剝離或裂紋的金屬膜。 如上所ϋ絲成無缺陷例如剝離的金屬膜和在支撐元 件和金屬膜間獲得優異的脫模性之間兩者只能選其一。因 297公釐） 4 五、發明説明（ 此’難以穩定地製造滿足上述兩條件的金屬膜。 發明概述 因此本务明一目的是提供一種能夠克服或減少上述問 題的金屬膜的製造方法。因&，本發明目的旨在同時滿足 自支撐7C件上優異脫模性的需求，又滿足藉真空薄膜成形Line V. Description of the invention (The peeling of the (further), can not be transferred to the ceramic green board, plus.. The metal film has not been transferred and remains on the supporting element, such as breakage or cracks, etc., these problems. The technology has not been completely overcome.: This unexamined patent, please refer to the bulletin 7.66G72, a technology, in which the first metal film is up to a thickness of about 0.1 micron. When the thickness reaches this thickness, the first all belongs to the film # Swim δ until the uniform hook continuous film. As described in the above literature, the size is 1 micron, usually 0 5 micrometers or larger, compared to the case where pinholes are formed. Bei Zhifeng: Fruit, although some in 1 x 105_2 These areas can form a homogeneous connection and other areas of 10 nm2 may become pinholes: two't 二 In some areas of 1 x 10W, only one or two edges of the pinhole can be seen, 1-< 1 point, and may become a condition where there is no metal film within this range „-In this white-know technology, the thermal method achieves the conditions shown in FIG. 5, where gold is an island structure in any area of 1 X 10W or Reticulated structure. Also: Miscellaneous Japanese unexamined patent applications The technical control described in Bulletin 7_66G72 is the so-called peel-off macroscopic control. Therefore, when conditions that exhibit strong decoupling are used, the problem is that it is used for the metal of the first metal film and the support-piece. Conditions for the formation of rhenium in the combination and film forming method. Due to the internal force generated in the part other than the pinholes in the gold: film during the process of plate formation, or during the rinsing process, or in the subsequent washing process, the metal film may = crack And the metal film may be peeled off, so it is difficult to form a metal film without defects such as peeling or cracking. The metal film reeled as above without defects such as peeling off the metal film and obtaining excellent releasability between the support member and the metal film Only one of them can be chosen. Because of 297 mm) 4. V. Description of the invention (It's difficult to stably manufacture a metal film that satisfies the above two conditions. Summary of the invention Therefore, the purpose of the present invention is to provide a method that can overcome or reduce the above problems. Method for manufacturing metal film. Because of &, the purpose of the present invention is to simultaneously satisfy the demand for excellent mold release on self-supporting 7C parts, and to satisfy the requirements of vacuum film forming
設備成膜期間，或藉金屬膜鍍膜或鍍膜後水洗期間不會發 生例如剝離和裂紋缺陷的需求。 曰X 本發明另一目的係提供疊層陶瓷電子元件，其包括採用 上述金屬膜製造方法製造的金屬膜，以及提供一種該陶兗 電子元件的製造方法。 根據本發明第一方面，提供一種金屬膜的製造方法，包 括·使用真空薄膜成形設備在支撐元件上形成由無電鍍催 化劑物質製得的第一金屬膜之第—步驟，該第一步係在第 一金屬膜生長成均勻連續膜之前完成；及利用第一金屬膜 作催化刈進行然電鍍的同時，藉由金屬形成膜而形成第二 金屬膜之第二步驟。 第金屬膜可為島嶼結構（島嶼階段）、網路結構（溝槽階 段5或孔2階段）、束形、或原子或分子形狀。金屬膜較好在〜x 10 nm的任何區域内為島嶼結構或網路結構，更好為島嶼 結構。 ^ 第一金屬膜較好含有至少一種選自鈀、銀、金、鉑、鎳 、鈷、鍺和銥的金屬。 第-金屬膜更好選自厚度小於1〇 nm的把膜、厚度小於 2〇 nm的銀膜和厚度小於2〇nm的金膜的金屬膜。 本紙張尺度it财s國家標準(CNiTT视格(2iG X 29Ϋ公楚) 574416 五、發明説明（ 第二金屬膜較好含有至少一種選自鎳、銅、銀、鈀、鉑 、始和錄的金屬。 本發明第二方面係提供一種金屬膜的製造方法，包括： 利用真工薄膜成形,又備在支撐元件上形成由無電鍍晶種物 貝衣成的第一金屬膜之第一步驟，該第一步驟係在第一金 屬膜生長爲均句連續膜之前完成；在由於對第一金屬膜至 >、表面上的離子置換反應而在採用浸潰式鐘膜的過程中因 黏合形成由無電鍍催化劑物質製得的第二金屬膜之第二步 驟，及利用第二金屬膜作催化劑進行無電鐘的同時，藉由 金屬形成膜而製成第三金屬膜之第三步驟。 以類似於第一方面的方式，第一金屬膜可為任何形式， 只要不是均勻連續膜即可。然而，該金屬膜較妤在丨X i〇5 nm2 的任何區域内為島嶼結構或網路結構，更好為島嶼結構。 較好，第一金屬膜含有至少一種選自銀、鋁、鎘、鈷、 銅、鉻、鐵、蘇、銦、猛、鎳、斜、錫和鋅的金^，及第 二金屬膜含有至少一種選自鈀、鉑、金、銀、铑和銥的金 屬’其為可替代含於第一金屬膜中的金屬之金屬。 更好’第一金屬膜為選自厚度小於3〇Γ1ιη的銅膜、厚度小 於20 nm的銀膜和厚度小於1〇 nm的鐵膜的金屬膜。 較好，第三金屬膜含有至少一種選自鎳、銅、銀、鈀、 鉑、鈷和铑的金屬。 不管在第一方面或第二方面中，爲了在第一金屬膜生長 成均勻連續膜之前完成第一步，較好控制第一步進行的時 間。 五、發明説明（ 6 ) 上述情況中，較好進行_製造步驟 相同成膜條件下藉由形成第—金相 第-步库 均勾連續膜的臨界時間，但又包 金屬膜生長i 其中選擇比該臨界時間更短的：二：條件除外’ 間。 瑪進仃苐一步驟的時 由掩模形成圖案。 件表面已進行脫模 較好，第—步驟中，第-金屬膜係藉 較好，其上形成第—金屬膜的支撺元 處理。 較好，支撐元件使用膜型支撐元件。 任何材料都可用作支撐元件， 、金屬或金屬氧化物。 使时機材枓、够 本發明亦提供一種藉上述任何梦 ^ 』衣以方法製造的金屬膜。 較好，該金屬膜係用於No requirements such as peeling and cracking defects occur during the film formation of the device or during metallization or after washing with metal. Another object of the present invention is to provide a laminated ceramic electronic component, which includes a metal film manufactured by using the above-mentioned metal film manufacturing method, and a method for manufacturing the same. According to a first aspect of the present invention, there is provided a method for manufacturing a metal film, including the first step of forming a first metal film made of an electroless catalyst material on a supporting member using a vacuum film forming apparatus, the first step being The first step of forming the first metal film into a uniform continuous film is completed; and the second step of forming a second metal film by forming a film from metal while using the first metal film as a catalyst to perform electroplating. The first metal film may be an island structure (island stage), a network structure (trench stage 5 or hole 2 stage), a beam shape, or an atomic or molecular shape. The metal film is preferably an island structure or a network structure in any region of ~ x 10 nm, and more preferably an island structure. ^ The first metal film preferably contains at least one metal selected from the group consisting of palladium, silver, gold, platinum, nickel, cobalt, germanium, and iridium. The -metal film is more preferably selected from a metal film having a thickness of less than 10 nm, a silver film having a thickness of less than 20 nm, and a metal film having a thickness of less than 20 nm. This paper is a national standard (CNiTT view grid (2iG X 29)) 574416 5. Description of the invention (The second metal film preferably contains at least one selected from nickel, copper, silver, palladium, platinum, The second aspect of the present invention is to provide a method for manufacturing a metal film, comprising: a first step of forming a first metal film formed by electroless seed coating on a support element by using a real film forming, This first step is completed before the first metal film is grown into a homogeneous continuous film; it is formed due to adhesion during the process of using the immersion bell film due to the ion replacement reaction on the surface of the first metal film to > The second step of the second metal film made of the electroless plating catalyst substance, and the third step of forming the third metal film by forming a film from metal while performing the electric clock without using the second metal film as a catalyst. In the manner of the first aspect, the first metal film may be in any form, as long as it is not a uniform continuous film. However, the metal film is more an island structure or a network structure in any region of X 105 nm2, Better for island Preferably, the first metal film contains at least one type of gold selected from the group consisting of silver, aluminum, cadmium, cobalt, copper, chromium, iron, thallium, indium, manganese, nickel, oblique, tin, and zinc, and a second metal. The film contains at least one metal selected from the group consisting of palladium, platinum, gold, silver, rhodium, and iridium, which is a metal that can be substituted for the metal contained in the first metal film. More preferably, the first metal film is selected from a thickness of less than 30. Γ1ιm copper film, silver film with a thickness of less than 20 nm, and metal film with an iron film with a thickness of less than 10 nm. Preferably, the third metal film contains at least one selected from the group consisting of nickel, copper, silver, palladium, platinum, cobalt, and rhodium Regardless of the first aspect or the second aspect, in order to complete the first step before the first metal film grows into a uniform continuous film, it is better to control the time of the first step. V. Description of the invention (6) The above situation Medium, it is better to carry out the critical time of forming the first-metallographic step-step homogeneous continuous film under the same film-forming conditions under the same manufacturing steps, but also including the growth of the metal film. Among them, choose a shorter time than the critical time: two : Except for the conditions. When a step is performed, the mask shape The surface of the part has been demolded. In the first step, the first metal film is better, and the first metal film is formed thereon. It is better that the supporting element is a film type supporting element. Any material can be used as the supporting element, metal, or metal oxide. The timing material is sufficient, and the present invention also provides a metal film manufactured by any of the above methods. Preferably, the metal film is used for
烕在宜層陶瓷電子元件内的 内部導電膜。 J =明又有關-種4層衫電子元件，其設有多個疊層 •曰及在陶究層間沿著特定介面延伸的内部導電膜。本 發明具體之此登層陶奢^ Ύ Tr rb 人商 尤電子70件中，内部導電膜係藉上述 金屬膜完成者。 哭上述疊層陶瓷電子元件的典型實施例包括多層陶瓷電容 本發明亦提供一種由上述製造方法製造且形成在支撐元 件上的金屬膜。按照下述方法將金屬膜塗佈在支撐元件上 進行本發明具體化之疊層陶瓷電子元件的製造方法。 本發明又提供疊層陶瓷電子元件的製造方法，包括利用 本紙張尺度通用巾® a家料(CNS) A4規格(21『 297公釐） 574416 A7 -------—- ______B7 五、發明説明（1 ] -----一~-- ::溥，成形设備在支撐元件上形成由無電鍍催化劑物質 ::仔的：一金屬膜，該成形係在第一金屬膜生長爲均勻連 續膜之前完成；利用第一金屬膜作催化劑進行無電鍵的同 時藉由金屬形成膜而形成第二金屬膜；藉由在支撐元件上 形成陶瓷生板以覆蓋金屬膜而形成包括金屬膜和陶瓷生板 的複合體；藉疊層多個複合體製造粗胚疊層體；自各複合 體上剝離支撐元件；及烘培粗胚疊層體。 本發明更進一步提供一種疊層陶瓷電子元件的製造方法 ，包括利用真空薄膜成形設備在支撐元件上形成由無電鍍 催化劑物質製得的第一金屬膜，該成形係在第一金屬膜生 長爲均勻連續膜之前完成；利用第一金屬膜作催化劑進行 無電鍵的同時藉由金屬形成膜而形成第二金屬膜；製造陶 竟生板’藉由將金屬膜從支撐元件上轉移到陶竟生板而製 造包括金屬膜和陶瓷生板的複合體；藉由疊層多個複合體 製造粗胚疊層體；及烘焙粗胚疊層體。 本發明更進一步提供一種藉上述製造方法製造的疊層陶 瓷電子元件。 如上述，本發明金屬膜製造方法具體例中，形成無電鍍 催化劑或晶種物質的第一金屬膜，使得其不會變成均勻連 續膜，且隨後，利用第一金屬膜作催化劑藉無電鍍形成第 二金屬膜。另外，藉由對於第一金屬膜的至少表面的離子 置換反應形成第二金屬膜而變爲無電鍍用之催化劑，隨後 ，利用該第二金屬膜作催化劑藉無電鍍形成第三金屬膜。 由於該方法，即使當採用支撐元件與金屬膜之組合或賦 -10- 本紙張尺度.適用中國國家標準(CNS) A4規格（210 X 297公釐) 五、發明説明（s 予金屬膜自支樓元件脫模優異性的成膜士 一 屬膜成形過程尹，或形成第_ Ί τ在弟一金 ^ 或弟二金屬膜的盔電铲釦苴 後的水洗過程t，金屬膜亦不合出 …鍍#八 个 '出現缺陷，例如剝離和裂 本發明具體化的金屬膜製造方法中，如上述， =屬膜無電鍍催化劑或晶種物質，使得其不會變成均句連 、，膜。測定何時成膜進行直到第—金屬膜生長爲均勾連續 膜’有時，在隨後無電錢或水洗過程中第一金屬膜剝離。、 然而’當成膜在第一金屬膜生長爲均勾連續膜之前完成時 ’第一金屬膜不會在隨後無電鑛或水洗過程中剝離。本發 明即基於該發現完成者。 x 上述現象（從前述發現所得）出現的原因據估計為，當第 一金屬膜不連續時，鍍膜亦即第二或第三金屬膜的内部應 力在無電鍍過程中由於某些原因鬆弛。 因此，當使用本發明的金屬膜製造疊層陶瓷電子元件時 ，可以可靠地達成金屬膜對陶瓷生板的優異轉移。轉移需 要的時間可縮短，此外，可改良疊層陶瓷電子元件的産 率 〇 本發明具體化的金屬膜製造方法中，當在1 X iMnm2的 任何區域内以島嶼結構或網路結構製成第一金屬膜時，即 使金屬膜是在可得到優異脫模性的上述條件下形成的，亦 可更可靠地得到防止缺陷出現的效果。 當在形成第一金屬膜中使用掩模，即使不進行例如光微 景々姓刻法和姓刻法的步驟，亦可製造有圖案的金屬膜，因 _ - 11 _ 本紙張尺度適财® s家標準(CNS) M規格(21G χ 297公寶) 574416导电 Internal conductive film inside the ceramic layer of the appropriate layer. J = related to Ming-a 4-layer shirt electronic component with multiple stacks • An internal conductive film extending along a specific interface between ceramic layers. In the present invention, the specific embodiment of the ceramic pottery ^ Tr rb, especially the electronic, 70 pieces, the internal conductive film is completed by the above-mentioned metal film. A typical embodiment of the above-mentioned laminated ceramic electronic component includes a multilayer ceramic capacitor. The present invention also provides a metal film manufactured by the above-mentioned manufacturing method and formed on a supporting member. A method for manufacturing a laminated ceramic electronic component embodying the present invention is carried out by applying a metal film to a support member according to the following method. The present invention also provides a method for manufacturing laminated ceramic electronic components, which includes the use of a paper-size universal towel® a household material (CNS) A4 specification (21 『297 mm) 574416 A7 ---------- ______B7 5. Description of the invention (1) ----- 一 ~-:: 溥, the forming equipment forms an electroless catalyst material on the supporting element :: a: a metal film, the forming system grows on the first metal film as The uniform continuous film is completed before; the first metal film is used as a catalyst to form a second metal film by forming a metal film without electrical bonding; and a ceramic green plate is formed on the support member to cover the metal film to form a metal film and A composite body of ceramic green sheets; a rough embryo laminate is produced by laminating a plurality of composite bodies; a supporting element is peeled from each composite body; and a rough embryo laminate is baked. The present invention further provides a laminated ceramic electronic component. A manufacturing method includes forming a first metal film made of an electroless catalyst material on a supporting element by using a vacuum thin film forming equipment, and the forming is completed before the first metal film is grown into a uniform continuous film; the first metal film is used as The catalyst is electroless-bonded while forming a second metal film by forming a metal film; manufacturing a ceramic green sheet 'by transferring a metal film from a supporting element to a ceramic green sheet to manufacture a composite including a metal film and a ceramic green sheet; A plurality of composite bodies are laminated to produce a rough embryo laminate; and a baked rough embryo laminate is provided. The present invention further provides a laminated ceramic electronic component produced by the above-mentioned manufacturing method. As described above, a specific example of the metal film manufacturing method of the present invention In the process, a first metal film of an electroless catalyst or a seed material is formed so that it does not become a uniform continuous film, and then a second metal film is formed by electroless plating using the first metal film as a catalyst. In addition, by An ion displacement reaction of at least the surface of a metal film forms a second metal film to become a catalyst for electroless plating, and then, the second metal film is used as a catalyst to form a third metal film by electroless plating. Because of this method, even when using The combination or support of supporting element and metal film -10- This paper size. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) V. It is clearly stated that the film-maker who has excellent mold release from the metal film self-supporting component is a film forming process Yin, or the formation of _ Ί τ after the helmet electric shovel buckle of the first metal ^ or the second metal film. In the water washing process, the metal film is not produced ... Defects in the plating # 8, such as peeling and cracking. In the method for manufacturing the metal film embodied in the present invention, as described above, = the film has no electroplating catalyst or seed material, making it unsuitable. Will become a uniform sentence, film. Measure when film formation is carried out until the first-metal film grows into a uniform continuous film 'Sometimes, the first metal film peels off in the subsequent electricity or water washing process. However,' When the film is formed in the first When a metal film is grown as a homogeneous continuous film before completion, the 'first metal film will not be peeled off during subsequent electroless ore or water washing. The present invention is based on the discovery of the finisher. x The reason for the above phenomenon (obtained from the foregoing findings) is estimated that when the first metal film is discontinuous, the internal stress of the plating film, that is, the second or third metal film, is relaxed for some reason during the electroless plating process. Therefore, when the laminated ceramic electronic component is manufactured using the metal film of the present invention, the excellent transfer of the metal film to the ceramic green sheet can be reliably achieved. The time required for the transfer can be shortened, and in addition, the yield of laminated ceramic electronic components can be improved. In the metal film manufacturing method embodied in the present invention, when an island structure or a network structure is made in any region of 1 X iMnm2, In the case of a metal film, even if the metal film is formed under the above-mentioned conditions where excellent releasability is obtained, the effect of preventing the occurrence of defects can be obtained more reliably. When a mask is used in the formation of the first metal film, a patterned metal film can be manufactured without performing steps such as photomicrography and surname engraving, because _-11 _ This paper size is suitable for financial ® s Home Standard (CNS) M Specification (21G x 297 Gem) 574416
此可簡化製造圖案金屬膜的步驟。 進行形成第-金屬膜的步驟的時間經控制 膜生長爲均勾連續膜之前完成。爲了測定料間 第-金屬膜生長爲均句連續獏的臨界時間。當選 界時間更短的時間作爲進行第一金屬膜成形步驟的時㈣ ，進行形成第一金屬膜的步驟的時間可易於決定。一曰 定該時間，在隨後金屬膜的製造中’可穩定开;：第：= 膜而不變成均句連續膜。 ' 圖式簡要說明 本發明具體例將藉下述實施例並參考後述圖式加以描述： 圖1A和1B係說明本發明金屬膜製造方法具體例的=視 圖，顯示包含在該製造方法中的典型步驟； 圖2為說明圖1A中所示的第一金屬膜2形成條件的進一 步放大剖視圖。 圖3A至3C為說明本發明的疊層陶瓷電子元件的製造方 法第一具體例剖視圖，及顯示包含於該製造方法中的典型 步驟； ^ 圖4Α至4C係說明本發明的疊層陶瓷電子元件的製造方 法第二具體例的剖視圖，並顯示包含在該製造方法中的典 型步驟。 ^ 圖5係貫驗1中製造的實施例1第一金屬膜的電子顯微辟 片。 一 較佳實施例描述 圖1Α及1Β及圖2說明本發明金屬膜製造方法的第—實施This can simplify the steps of manufacturing a patterned metal film. The time for performing the step of forming the first metal film is controlled before the film is grown to a uniform continuous film. In order to determine the critical time for the first-metal film to grow in a continuous sentence. When the selection time is shorter as the time when the first metal film forming step is performed, the time when the first metal film forming step is performed can be easily determined. As soon as this time is fixed, in the subsequent production of the metal film, ′ may be stably opened; the:: film without becoming a uniform sentence continuous film. Schematic description of specific examples of the present invention will be described by the following examples and with reference to the following drawings: Figures 1A and 1B are = views illustrating specific examples of the method of manufacturing the metal film of the present invention, showing typical examples included in the manufacturing method Steps; FIG. 2 is a further enlarged cross-sectional view illustrating conditions for forming the first metal film 2 shown in FIG. 1A. 3A to 3C are cross-sectional views illustrating a first specific example of a method for manufacturing a laminated ceramic electronic component according to the present invention, and show typical steps included in the manufacturing method; ^ FIGS. 4A to 4C illustrate the laminated ceramic electronic component according to the present invention. A cross-sectional view of a second specific example of the manufacturing method and shows typical steps included in the manufacturing method. ^ FIG. 5 is an electron micrograph of the first metal film manufactured in Example 1 in Example 1. DESCRIPTION OF A PREFERRED EMBODIMENT FIGS. 1A and 1B and FIG. 2 illustrate a first embodiment of a method for manufacturing a metal film according to the present invention.
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例。 關於製造目標金屬膜，如圖1A所示，進行第一步驟，即 矛！用真工薄膜成形設備在支撐元件上形成由變爲無電鑛催 化劑的材料製得的第一金屬膜2。本文中，較好使用掩模3 第一金屬膜2藉由該掩模3形成第一金屬膜2而形成圖案。 上述真空薄膜成形設備實例包含真空蒸發設備，濺射設 備釦射切除设備，離子鍍膜設備，聚集離子束設備及mbe 設備。 有機材料、碳、金屬或金屬氧化物可使用作為支撐元件1 的材料。較好，支撐元件丨具有其上欲形成第一金屬膜2的 表面，該表面已進行脫模處理。當相對於第一金屬膜2具有 低黏著力的物質作爲支撐元件1的材料時，可省略支撐元件 1的表面脫模處理。 例如’當有機材料例如氟樹脂或矽樹脂使用作為支撐元 件1的材料時，即使省略脫模處理亦可賦予優異的脫模性。 支撐元件1可為具有相對高硬度的板形，或是具有柔韌性 的膜形。 當支撐元件1為膜形時，由於它可捲繞成捲，可簡化生産 設備的構造，其中連續製造金屬膜，此外，能夠預期高的 生產率。此外，如果金屬膜大量生産由於可降基儲存空間 ’以及當製造的金屬膜運輸時可降低重量和體積，而可降 低儲存費用和運輸費用。 當使用膜型支撐元件1時，通常爲聚對苯二甲酸乙二製 成者（其均等於陶瓷生板模製過程中使用的載體膜），且可 -13 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐）example. Regarding the manufacturing of the target metal film, as shown in FIG. 1A, the first step, that is, spear! A first metal film 2 made of a material that becomes a galvanic catalyst is formed on a supporting member using a real-world film forming apparatus. Herein, it is preferable to use the mask 3 and the first metal film 2 to form a pattern by forming the first metal film 2 with the mask 3. Examples of the above-mentioned vacuum film forming equipment include vacuum evaporation equipment, sputter equipment, ejection and ablation equipment, ion coating equipment, focused ion beam equipment, and mbe equipment. Organic materials, carbon, metals, or metal oxides can be used as the material of the support member 1. Preferably, the supporting member 丨 has a surface on which the first metal film 2 is to be formed, and the surface has been subjected to a demolding treatment. When a substance having a low adhesive force with respect to the first metal film 2 is used as the material of the support member 1, the surface release treatment of the support member 1 may be omitted. For example, when an organic material such as a fluororesin or a silicone resin is used as the material of the support member 1, even if the release treatment is omitted, excellent release properties can be imparted. The support member 1 may be a plate shape having a relatively high hardness, or a film shape having a flexibility. When the support member 1 is in the shape of a film, since it can be wound into a roll, the structure of a production facility can be simplified, in which a metal film is continuously manufactured, and further, high productivity can be expected. In addition, if the mass production of the metal film can reduce the storage space and the weight and volume when the manufactured metal film is transported, the storage cost and transportation cost can be reduced. When using the film-type support element 1, it is usually made of polyethylene terephthalate (all of which are equal to the carrier film used in the molding process of the ceramic green board), and can be -13-This paper size applies to Chinese national standards (CNS) A4 size (210 X 297 mm)
裝 訂Binding
至 >、種選自、銀、金 '鉑 錄、始、姥和銀的金 為欲轉化之陶奢+ ★ 體膜表面進行i樹广中使用的載體膜。此時，較好索 於膜形支撑 日切樹脂之脫模處理以易於剝離。j 亦可使用：：:，材::除了聚對笨二曱酸乙二醋之外 等製成的膜。/、可使用由除了有機膜之外之不銹· Y以:為構成欲變爲無電鍍催化劑的第一金屬膜2的物 該等金屬可單獨使用或使用含該等金屬的合金。 爲了達到k異催化性，必須防止由於氧化層形成引起 =化。因此，第一金屬膜2形成後，必須迅速地進行下述 v4控制防止氧化層形成。從易於進行控制的 觀之車乂好使用貴金屬。其中，把由於其相對於各種 膜溶液之高催化性因而較宜。處理除去鈍化層後進行下 無電錢亦有效。 本發明具體例中，重要地是形成第一金屬膜的第一步驟 係在第一金屬膜2生長爲均勻連續膜之前完成。 如圖2所示，第一步驟所形成的第一金屬膜2可為任何形 狀只要不是均勾連續膜即可。例如第一金屬膜可為島嶼結 構（島嶼階段）、網路結構（溝槽階段或孔階段）、原子形狀、 分子形狀、束狀等。特佳為第一金屬膜2在1 X 1〇5 nm2的任 何區域内非均勻連續膜。第一金屬膜2的形狀較好為島嶼結 構或網路結構，更好為島嶼結構或溝槽階段的網路結構， 最佳為島樓結構。 通常，在薄膜生長過程令，原子依序到達支撐元件、遷 -14- 本纸張尺度適用中國國家標準(CNS) A4規格(210X297公釐)To >, a kind of gold selected from the group consisting of silver, gold, platinum, silver, gold, and silver. In this case, it is preferable to release the film-shaped support for the day-cut resin to facilitate peeling. j It is also possible to use :: ,, material :: in addition to polyethylene terephthalate, etc. / 、 Stainless steel other than organic film can be used. Y: It is used to constitute the first metal film 2 to be an electroless plating catalyst. These metals can be used alone or an alloy containing these metals can be used. In order to achieve the k-catalytic property, it is necessary to prevent the formation of oxides due to the formation of an oxide layer. Therefore, after the first metal film 2 is formed, the following v4 control must be performed quickly to prevent the formation of an oxide layer. Use precious metals from an easy-to-control viewpoint. Among them, it is preferable because of its high catalytic activity with respect to various membrane solutions. After the passivation layer is removed, no electricity is also effective. In the specific example of the present invention, it is important that the first step of forming the first metal film is completed before the first metal film 2 is grown into a uniform continuous film. As shown in Fig. 2, the first metal film 2 formed in the first step may be of any shape as long as it is not a uniform continuous film. For example, the first metal film may be an island structure (island stage), a network structure (trench stage or hole stage), atomic shape, molecular shape, bundle shape, and the like. Particularly preferred is a non-uniform continuous film of the first metal film 2 in any region of 1 X 105 nm2. The shape of the first metal film 2 is preferably an island structure or a network structure, more preferably an island structure or a network structure at a trench stage, and most preferably an island building structure. Usually, during the film growth process, the atoms arrive at the supporting elements in sequence and migrate. -14- This paper size applies to China National Standard (CNS) A4 (210X297 mm)
12 五、發明説明（ 移、晶種形成、晶種生長及凝集。生長爲均 結構和網路結構階段發生的。生長爲均勻連ΐ:藉 ==膜條件而異，例如欲黏合的材料 件的種神條件，以及真空薄膜形成設備中二^ 然而，通常，當厚度達到最大的條件。 二。本發明人的試驗顯示，當對於絶、銀、銅、全丄 2〇度分別變爲10⑽或更大、2。_或更大、3〇 ’ 2一更大及1〇⑽或更大時，對幾乎任—種支揮元更件大; 秦發條件，蒸發膜料生長爲均W㈣。^凡件和 因此’當進行本發明金屬膜的製造方法時 行製造步驟，J：中決定忐胺玫从 預先進 ” 成腠條件。除了時間條件之外，点 勝條件還可包括例如構成第一金 卜成 真空缚膜成形設備中設定的條件。在該決定的成膜 條件下’形成第一金屬膜2，並因此找到.第一金屬 、 爲均勻連續膜所需的臨界時間。 ' 、 ^ 時生產中’形成第一金屬膜2的第-步驟進行的 上述製造步驟中發現的臨界時間。當膜連續地在 ==向製造時而變成該支撐元件時，上述時間係藉 ΠίίΓ控制。然而’事實上’第-金屬膜2必需以 化劑晶種。 U鍍步驟中作為無電鍍催 如圖1Β所示’形成第二金屬膜4的第二步驟之進行係利用 第-金屬膜2作為催化劑進行無電錄的同時由特定金屬製 成膜者。 ___ -15- 本紙張尺度適財g g家標準(CNS) Μ規格(咖χ撕公登) _____ 五、發明説明（13 形成第二金屬膜4的無電鍍中，使用無電鍍槽。其可包括 例如至少一種選自鎳、銅、銀、鈀、始、鈷和鍺所組1之 金屬組群。 該第二金屬膜4構成所得金屬膜的關鍵部分。從導電性、 成本等方面看，第二金屬膜4宜由銅或鎳組成，其中該金屬 膜被用作疊層陶曼電子元件的内部導電膜，#進行^梦 造疊層陶瓷電子元件時可能應用還原氣氛。此時，例二： 電銅鍍槽、無電鎳-磷合金電鍍槽、和無電鎳-硼合金電鍍 槽可以作為無電鍍槽。 又 另一方面，若不可能在烘焙階段應用還原氣氛來製造疊 層陶瓷電子元件，則第二金屬膜4係由銀、鈀、鉑或其合： 所組成。 〃 可以使用上述各種金屬與其他金屬元素混合製成的合金 作為類低共熔體。此外，可使用鈷·磷、鈷·硼、鍺番 如圖1A所示，第-步驟中，使用掩模3形成第_金屬膜: ’由此對第-金屬膜2形成圖案。因此，當在第二步驟中進 行無電鍍時，第二金屬膜4僅在其上形成有第一金屬膜之的 部分上形成，因此金屬膜可整體形成圖案。至於此掩模3 ’例如可使用金屬掩模和各種遮蔽膜。 述方法。使用各 。其中在第一金 二金屬膜4形成 形成圖案的方法並不限於使用掩模3的上 種保護膜的方法，例如可使用光致抗蝕劑 屬膜2形成後進行蝕刻的方法，和其中在第 後進行蝕刻的方法亦可。12 V. Description of the invention (Migration, seed formation, seed growth and agglutination. Growth occurs at the stage of homogeneous structure and network structure. Growth is uniform flail: depending on the membrane conditions, such as material pieces to be bonded However, in general, when the thickness reaches the maximum condition. Second, the inventor's experiments show that when the absolute, silver, copper, and full 丄 20 degrees become 10⑽, respectively Or larger, 2. _ or larger, 30 ′ 2 to larger, and 10⑽ or larger, the size of almost any kind of branch is larger; in the case of Qinfa, the evaporation film material grows evenly. ^ Every piece and therefore 'when performing the manufacturing method of the metal film of the present invention, the manufacturing steps are performed, and J: determines the 忐 amine rose from pre-advanced "into 除了 conditions. In addition to the time conditions, the point win conditions may include, for example, the composition The conditions set in the first Jinbu vacuum forming film forming equipment. Under the determined film forming conditions, 'the first metal film 2 is formed, and thus found. The first metal, the critical time required for a uniform continuous film.' The first metal film 2 is formed during production The critical time found in the above-mentioned manufacturing step performed in the first step. When the film becomes the supporting element continuously during the manufacturing of the ==, the above time is controlled by ΠίίΓ. However, the 'fact' first-metal film 2 must be Seeding agent of the chemical agent. As the electroless plating catalyst in the U plating step, as shown in FIG. 1B, the second step of forming the second metal film 4 is performed by using the first metal film 2 as a catalyst for electroless recording and made of a specific metal. ___ -15- The paper size is suitable for gg home standard (CNS) M specifications (Ca χ tear publicly registered) _____ V. Description of the invention (13) In the electroless plating for forming the second metal film 4, an electroless plating tank is used. It may include, for example, at least one metal group selected from the group 1 of nickel, copper, silver, palladium, starting, cobalt, and germanium. The second metal film 4 constitutes a key part of the resulting metal film. In terms of conductivity, cost, etc. Seeing, the second metal film 4 should preferably be composed of copper or nickel, wherein the metal film is used as the internal conductive film of the laminated Taoman electronic component, and a reducing atmosphere may be applied when making a laminated ceramic electronic component. At this time , Example 2: Electric copper plating tank, no Nickel-phosphorus alloy plating baths and electroless nickel-boron alloy plating baths can be used as electroless plating baths. On the other hand, if it is not possible to apply a reducing atmosphere during the baking stage to manufacture laminated ceramic electronic components, the second metal film 4 series It is composed of silver, palladium, platinum, or a combination thereof: 〃 An alloy made of a mixture of the above metals and other metal elements can be used as a eutectic-like melt. In addition, cobalt · phosphorus, cobalt · boron, and germanium can be used. As shown in FIG. 1A, in the first step, the third metal film is formed using the mask 3: 'The first metal film 2 is thus patterned. Therefore, when electroless plating is performed in the second step, the second metal film 4 It is formed only on the portion where the first metal film is formed, so that the metal film can be patterned as a whole. As the mask 3 ′, for example, a metal mask and various shielding films can be used. Mentioned method. Use each. The method for forming the pattern on the first gold-metal film 4 is not limited to the method using the upper protective film of the mask 3, for example, a method of etching after the photoresist-based film 2 is formed, and The method of performing etching after that may be used.
本紙張尺度適财國國家鮮(CNS).A4規格(210 574416 A7 _________B7 五、發明説明（14 ) 然而’從簡化方法的角度看，使用掩模3例如金屬掩模的 方法較有利，因為掩模3可容易地黏附或分離，可重復使用 及在第一金屬膜2已經形成的階段即可達到形成圖案的條 件。 貫施本發明金屬膜的製造方法亦可按照下述方法進行。 在第二具體例中，在支撐元件上形成第一金屬膜之第一 步驟使用真空薄膜成形設備。一種物質作爲形成第一金屬 膜的材料，所述第一金屬膜變爲無電鍍晶種但對無電鍍不 具催化性。 該第一步驟係在第一金屬膜生長爲均勻連續膜之前完成 。此類似於第一具體例。第一金屬膜較好在i χ 1〇5nm2的 任何區域内為島嶼結構或網路結構。此亦類似於第一具體 例。 隨後，作爲無電鍍催化劑的材料用以替代欲變爲藉浸潰 式鍍膜進行無電鍍的晶種的第一金屬膜的表面或全部，由 此進行开乂成第一金屬膜的第一步驟。該第二金屬膜係.由於 上述與第一金屬膜的至少表面的離子置換反應所形成。因 此，類似於第一金屬膜的方式，未形成均勻連續膜。 更詳言之’該第二步驟中’將其上形成有第一金屬膜的 支撑疋件浸潰在對無電鍍溶液具有催化性的金屬溶液中。 由於該浸潰條件下氧化還原平衡電位的不同而進行取代反 應’形成第二金屬膜。因此’有必要使構成第一金屬膜的 金屬的氧化還原平衡電位比構成第二金屬膜的金屬的平衡 電位更活性。相反，構成第二金屬膜的金屬的氧化還廣平 -17- 574416 五、發明説明（15 ) 衡電位比構成第-金屬膜的金屬的氧化還原電位更惰性也 是必要的。 如上所述，第-金屬膜相對於無電鍍溶液來說未必具有 催化性。它可以由例如至少一種選自銀、在呂、鎘、鈷、銅 、鉻、鐵、鎵、銦、錳、鎳、鉛、錫和鋅的金屬組成。 這些金屬中，鎘、鉛、錫和鋅具催化劑毒性，因此當需 要有光澤膜時，較好使用不同金屬。 另一方面，氯化鈀•鹽酸水溶液等可作為具有催化性的金 屬溶液，用於形成第二金屬膜。該溶液通常作為預處理無 電鍍的活化溶液。事實上，其他具有催化性的金屬中，可 以使用比構成第一金屬膜的材料具有更惰性的氧化還原平 衡電位者。亦即該等可取代包括在第一金屬膜中的金屬的 金屬。例如，可以使用鉑、金、銀、铑、和銦以及鈀。 舉例作爲包含在第一或第二金屬膜中的金屬可單獨使用 ，或使用含有該等金屬的合金。 形成第三金屬膜的第三步驟係利用上述第二金屬膜作催 化劑進行無電鍍的同時藉由金屬形成膜進行者。由於在上 述第一具體例中，該第三步驟對應於形成第二金屬膜4的第 二步驟，且實質上類似於此，因此上述解釋也適用。 如上所述，第一和第二具體例中製造的金屬膜可有利地 用於形成疊層陶瓷電子元件的内部導電膜，例如形成多層 陶瓷電容器電容的内部電極。 圖3A至3C顯示根據本發明製造鲞層陶瓷電子元件的尠 造方法的第具體例。 、衣 574416This paper is suitable for the National Fresh (CNS) .A4 specification (210 574416 A7 _________B7 of the rich countries) V. Description of the invention (14) However, from the perspective of a simplified method, the method using a mask 3 such as a metal mask is more advantageous because the mask The mold 3 can be easily adhered or separated, and can be used repeatedly and the pattern forming condition can be achieved at the stage where the first metal film 2 has been formed. The method for manufacturing the metal film according to the present invention can also be performed according to the following method. In two specific examples, the first step of forming the first metal film on the support member uses a vacuum film forming apparatus. A substance is used as a material for forming the first metal film, and the first metal film becomes an electroless seed crystal but no Electroplating is not catalytic. This first step is completed before the first metal film is grown into a uniform continuous film. This is similar to the first specific example. The first metal film is preferably an island structure in any area of i x 105 nm2 Or network structure. This is also similar to the first specific example. Subsequently, as a material for the electroless plating catalyst, it is used to replace the first metal film that is to be changed into a seed crystal for electroless plating by the immersion plating film. The surface or the entire surface of the first metal film is thus formed. The second metal film is formed by the above-mentioned ion displacement reaction with at least the surface of the first metal film. Therefore, it is similar to the first metal film. In the method of the metal film, a uniform continuous film is not formed. More specifically, in the “second step”, the support member on which the first metal film is formed is immersed in a metal solution that is catalytic to the electroless plating solution. The substitution reaction proceeds due to the difference in redox equilibrium potential under this immersion condition 'to form a second metal film. Therefore,' it is necessary to balance the redox equilibrium potential of the metal constituting the first metal film with the metal constituting the second metal film. The potential is more active. On the contrary, the oxidation of the metal constituting the second metal film is also flat -17- 574416 V. Description of the invention (15) It is also necessary that the equilibrium potential is more inert than the redox potential of the metal constituting the first metal film. As above The first metal film is not necessarily catalytic relative to the electroless plating solution. It may be made of, for example, at least one selected from the group consisting of silver, zinc, cadmium, cobalt, copper, chromium, iron, and gallium. , Indium, manganese, nickel, lead, tin, and zinc. Among these metals, cadmium, lead, tin, and zinc are toxic to catalysts, so when a glossy film is required, different metals are preferred. On the other hand, chlorine Palladium-hydrochloric acid aqueous solution can be used as a catalytic metal solution to form a second metal film. This solution is usually used as an activation solution for pre-treatment electroless plating. In fact, other catalytic metals can be used in specific ratios. The material of the first metal film has a more inert redox equilibrium potential. That is, these can replace metals included in the first metal film. For example, platinum, gold, silver, rhodium, and indium, and palladium can be used. For example, the metal contained in the first or second metal film may be used alone, or an alloy containing these metals may be used. The third step of forming the third metal film is electroless plating using the second metal film as a catalyst. At the same time, the film is formed by a metal. Since the third step corresponds to the second step of forming the second metal film 4 in the first specific example described above, and is substantially similar to this, the above explanation also applies. As described above, the metal films manufactured in the first and second specific examples can be advantageously used to form an internal conductive film of a laminated ceramic electronic component, such as an internal electrode of a multilayer ceramic capacitor capacitor. Figs. 3A to 3C show a first specific example of a method of fabricating a cladding ceramic electronic component according to the present invention. Clothing 574416
圖3 A中，藉本發明金屬膜製造方法的第一或第具體例製 造的金屬膜11如所示係在支撐元件12上形成。如圖3A所示 ，金屬膜Π係在支撐元件1 2上形成的條件下進行處理。 如圖3B所示，爲了覆蓋金屬膜丨丨，藉由將陶兗生板^模 製在支撐it件12上，製造由金屬膜11#"旬瓷生板"組成的 複合體14。 ，如圖3C所示，粗胚疊層體15係藉由疊層多個複合體丨斗而 製成。圖3C顯示複合體14疊層過程的中間階段，附圖中僅 表示部分粗胚疊層體。圖3A||示優先對位於最上面位置之 複合體14進行。 如圖3C所示，複合體14以支樓元件作背概直到它被疊層 在預先疊層的複合體14上。因此’每次疊層複合體14，如 箭頭16所不，#由從支樓元件12—側施加壓力將多個複合 體Η重復壓黏在-起。此後，如箭㈣所示，冑支撑元件 12剝離。In FIG. 3A, a metal film 11 manufactured by the first or first specific example of the metal film manufacturing method of the present invention is formed on a support member 12 as shown. As shown in FIG. 3A, the metal film Π is processed under the conditions formed on the support element 12. As shown in FIG. 3B, in order to cover the metal film, a composite body 14 composed of a metal film 11 # " Xun porcelain green plate " is manufactured by molding a ceramic green sheet on the supporting it member 12. As shown in FIG. 3C, the rough embryo laminate 15 is made by laminating a plurality of composite bodies. Fig. 3C shows an intermediate stage of the lamination process of the composite 14, and only a part of the rough embryo laminate is shown in the drawing. Fig. 3A || shows that the complex 14 in the uppermost position is preferentially performed. As shown in Fig. 3C, the composite body 14 is based on a supporting element until it is laminated on the pre-laminated composite body 14. Therefore, 'each time the composite body 14 is laminated, as shown by the arrow 16', a plurality of composite bodies are repeatedly pressed together by applying pressure from the side of the supporting element 12. Thereafter, the cymbal support member 12 is peeled as shown by the arrow ㈣.
裝 訂 剝離支撐元件12的步驟可在疊層各複合 進行。 體14的步驟之前The step of binding and peeling the support member 12 may be performed by laminating each of the layers. Body 14 steps before
胚疊層體1 5時，沿著金 屬膜1 1與陶瓷生板1 3彼 屬 此 當用於製造多層陶瓷電容器的粗 膜11排列以便於藉疊層步驟中金 面對形成電容的内部電極之構成 爲了製造用於個別叠層陶荼I^ i增闹尤電子兀件的疊層晶片，切 粗肢疊層體15。若需要’其後進行脫脂步驟和"吾步驟 在供培的疊層體外表面形成端電極等，因此究 目標登層陶瓷電子7L件例如多層陶瓷電容器。When the embryo multilayer body 15 is arranged along the metal film 11 and the ceramic green plate 1 3, the rough film 11 used for manufacturing the multilayer ceramic capacitor is arranged in order to form the internal electrode of the capacitor by the gold surface in the lamination step. The structure is used to manufacture laminated wafers for individual laminated ceramics and electronic components, and the limb stack 15 is cut into thick pieces. If necessary, a degreasing step and a "step" are performed to form terminal electrodes on the outer surface of the laminated body to be cultured. Therefore, the target is a ceramic electronic 7L component such as a multilayer ceramic capacitor.
574416 A7 五、發明説明574416 A7 V. Description of the invention
圖4A至4C為說明解釋根據本發明疊層陶瓷電子元件製 造方法的第一具體例簡圖。 圖4A中，顯示以類似於同1 Λ w 彳於圖3A所不的方式，將金屬膜21形 成在支撐元件22上。 圖4A中，帛示模製在載體膜23上的陶究生板 如上所述，分別製造形成在支撑元件22上&金屬膜21和 模壓在載體膜23上的„生板24，此後，依次進行下列步 驟。 如圖4B所不，形成金屬膜21和陶瓷生板以的複合體25的 步驟係藉由將金屬膜21從支撐元件22上轉移到陶堯生板24 上進行者。 具體吕之，將形成在支撐元件22之金屬膜21及由載體膜 23支撐的陶瓷生板24彼此重疊，該條件下，支撐元件22和 載體膜23按照重疊的方向施壓。隨後，支撐元件22按照箭 頭26所不方法剝離，由此，金屬膜21從支撐元件22上轉移 到陶瓷生板24上。 如圖4C所不，形成陶瓷生板27的步驟是藉由疊層多個複 合體25所完成。圖4C中，類似於圖3C，圖中僅表示部分粗 胚疊層板27，圖中顯示對位於上面位置的複合體25優先疊 層。 複合體25藉載體膜23支撐直到被疊層在先前疊層的複合 體25上。因此，複合體25疊層後，按照箭頭28所示，從載 體膜23—側施加壓力，複合體25彼此重復壓結，隨後，載 體膜23按照箭頭29所示方向剝離，由此製造了粗胚疊層體4A to 4C are diagrams illustrating a first specific example explaining a method for manufacturing a laminated ceramic electronic component according to the present invention. In Fig. 4A, it is shown that the metal film 21 is formed on the support member 22 in a manner similar to that of Fig. 3A. In FIG. 4A, the ceramic green sheet molded on the carrier film 23 is shown above, and the metal sheet 21 formed on the support element 22 and the green sheet 24 molded on the carrier film 23 are manufactured separately. Thereafter, The following steps are performed in order. As shown in FIG. 4B, the step of forming the composite body 25 of the metal film 21 and the ceramic green sheet is performed by transferring the metal film 21 from the support member 22 to the Tao Yaosheng board 24. Specifically, Lu That is, the metal film 21 formed on the support member 22 and the ceramic green plate 24 supported by the carrier film 23 are overlapped with each other. Under this condition, the support member 22 and the carrier film 23 are pressed in the overlapping direction. Subsequently, the support member 22 The arrow 26 does not peel, and thus the metal film 21 is transferred from the support member 22 to the ceramic green sheet 24. As shown in FIG. 4C, the step of forming the ceramic green sheet 27 is by laminating a plurality of composites 25 Completed. In FIG. 4C, similar to FIG. 3C, the figure only shows a part of the rough embryo laminated plate 27, and the figure shows that the composite 25 located at the upper position is preferentially laminated. The composite 25 is supported by the carrier film 23 until it is laminated On the previously laminated composite 25. Therefore, the After the composite body 25 is laminated, pressure is applied from the carrier film 23 side as shown by arrow 28, and the composite bodies 25 are repeatedly entangled with each other. Subsequently, the carrier film 23 is peeled in the direction shown by arrow 29, thereby manufacturing a rough embryo laminate. body
574416 18 五、發明説明（ 27 〇 行剝離載體膜23的步驟可在疊層各複合體25的步驟之前進 上ΐ第一具體例的方式中，將所製得之粗胚疊層 體刀開，右茜要，進行脫脂和㈣ =等，由此製成目標疊—元件例如多:陶: :本發明具體例可應用於疊層陶究電子元件，例如多層陶 瓷支撐兀件’豐層陶瓷感應器’和疊層篩檢程式，以及多 層陶瓷電容器。 接著，描述試驗，該試驗係爲了證實本發明具體例的效 果所進行者。 試驗1 試驗1中，分別進行有關金屬膜製造方法的實施例和比較 例，以及對其作出評價。 1 ·實施例1 (1) 製造由聚對苯二甲酸乙二酯製成的膜作支撐元件，在 其上形成矽氧為主的脫模層。製造由厚度0.2 mm的不銹鋼 製成的金屬掩模，在其上於將變爲多層陶瓷電容器的多個 内部電極的部分設有開口。 (2) 將上述金屬掩模緊密黏合在支撐元件表面，該表面上 形成有脫模層。利用真空蒸發設備藉由該金屬掩模，以石 英β自振益厚度計爲基準的成膜速率爲1 A/sec共進行1〇秒， 藉由蒸發鈀在金屬掩模開口上形成第一金屬膜。 -21 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 574416 A7 B7 五、發明説明（ 用電子顯微鏡（TEM)觀察由鈀形成的第一金屬膜，其證 明鈀在1 X l〇5nm2的任何區域内係以島嶼結構存在。 圖5為上述第一金屬膜的電子顯微鏡照片。圖$中，參考 號1表示支撐元件，參考號2表示第一金屬膜。 (3)將其上形成有第一金屬膜的支撐元件浸入使用磷酸 作還原劑的無電鑛鎳-填合金錢槽中形成第二金屬膜。在該 典電鍍中，槽溫爲8〇°C，浸入時間爲5〇秒。 由此形成的金屬膜厚度爲0·7微米。 該金屬膜無缺陷且具有優異脫模性。 2 ·實施例2 (1) 製造類似於實施例丨之（1)的支撐元件和金屬掩模。 (2) 將上述金屬掩模緊密黏合到上述支撐元件的脫模層 一側表面上。利用真空蒸發設備藉由該金屬掩模，以石英 譜振器厚度計爲基準的成膜速率爲2 A/see共進行1()秒，藉 由蒸發鐵在金屬掩模開口上形成第一金屬膜。 用電子顯微鏡（TEM)觀察由鐵形成的第一金展膜，其證 明存在的鐵在1 X l〇5nm2的任何區域内為島嶼結構。 (3) 藉由將其上形成有第一金屬膜的支撐元件浸潰在氣 化鈀·鹽酸水溶液1分鐘，用鈀置換由鐵製成的第一金屬膜 的表面，由此形成由鈀製成的第二金屬膜。 (4) 將其上形成有第二金屬膜的支撐元件浸潰在類似於 貫施例1的步驟（3)的無電鍍鎳-磷合金鍍槽中，並維持類似 的浸潰時間，因此，藉無電鍍形成第三金屬膜。 所形成的金屬膜厚度爲0.7微米。 _____ _ 22 - &張尺度適用中國國家標準(CNS)^4規格(210 X 297公釐) 20 五、發明説明（ 該金屬膜無缺陷且具有優異脫模性。 3.實施例3 ⑴製造類似於實施例丨之⑴的支撐元件和金屬掩模。 ⑺將上述金屬掩模緊密黏合到上述支撐元件的脫模層 一側表面上。利用真空蒸發設備藉該金屬掩模，以石英諧 振器厚度計爲基準的成膜速率爲6 A/sec蒸發銀共進行⑽ ’在金屬掩模開口上形成第一金屬膜。 用電子顯微鏡（TEM)觀察由銀形成的第一金屬膜，其證 明存在的第一金屬膜幻x 1〇W的任何區域内為島墟处 構。 ^ m (3)將其上形成有第一金屬膜的支撐元件浸潰在類似於 實施例1的步驟（3)的無電鍍鎳磷合金鍍槽中，並維持與其 類似的浸潰時間，由此藉無電鍍形成第二金屬膜。 由此形成的金屬膜厚度爲〇·6微米。 該金屬膜無缺陷且具有優異脫模性。 4 ·實施例4 (1) 製造類似於實施例丨之（1)的支撐元件和金屬掩模。 (2) 將上述金屬掩模緊密黏合到上述支撐元件的脫模層 一側表面上。利用真空蒸發設備藉該金屬掩模，以石英諸 振為厚度計爲基準的5 A/sec的成膜速率蒸發銀10秒，在金 屬掩模開口上形成第一金屬膜。 用毛子顯微鏡（TEM)觀察由銀形成的第一金屬膜，其證 明存在的第一金屬膜在1 x 1〇5 nm2的任何區域内為島嶮么士 才冓。 ° 21 五、發明説明（574416 18 V. Description of the invention (27) The steps of peeling the carrier film 23 can be carried out before the step of laminating the composites 25 in the first specific example, and the obtained rough embryo laminate is cut open. , You Qian Yao, degreasing and ㈣ =, etc., thereby making the target stack-components such as: Pottery :: The specific examples of the present invention can be applied to laminated ceramic electronic components, such as multilayer ceramic support elements' Fung layer ceramics Inductors', laminated screening programs, and multilayer ceramic capacitors. Next, a test will be described. This test is performed to verify the effect of a specific example of the present invention. Test 1 In Test 1, the implementation of a method for manufacturing a metal film was performed separately. Examples and Comparative Examples, and evaluations thereof. 1 · Example 1 (1) A film made of polyethylene terephthalate was produced as a support element, and a silicon oxide-based release layer was formed thereon. Manufacture a metal mask made of stainless steel with a thickness of 0.2 mm, and provide an opening in a portion of a plurality of internal electrodes that will become a multilayer ceramic capacitor. (2) Adhere the above metal mask tightly to the surface of the supporting element, On the surface A mold release layer was formed. A vacuum deposition device was used for the metal mask to form a film at a rate of 1 A / sec based on the quartz β self-resonance thickness for a total of 10 seconds, and the metal mask was evaporated by palladium. The first metal film is formed on the opening. -21 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 574416 A7 B7 5. Description of the invention (observe the first formed by palladium with an electron microscope (TEM) Metal film, which proves that palladium exists as an island structure in any area of 1 × 105 nm2. Figure 5 is an electron microscope photograph of the first metal film described above. In the figure, reference number 1 indicates the support element, and reference number 2 indicates The first metal film. (3) The support member having the first metal film formed thereon is immersed in an electroless nickel-filled alloy money tank using phosphoric acid as a reducing agent to form a second metal film. In this typical electroplating, the bath temperature is 80 ° C, immersion time is 50 seconds. The thickness of the metal film thus formed is 0.7 micron. The metal film is defect-free and has excellent mold release properties. 2 · Example 2 (1) Manufacturing was similar to the example (1) The supporting element and metal mask of (1) (2) The metal mask is tightly adhered to the surface of one side of the release layer of the supporting element. A vacuum evaporation device is used to perform the film formation rate based on the thickness of the quartz spectrometer at a rate of 2 A / see. 1 () seconds, forming a first metal film on the opening of the metal mask by evaporating iron. Observing the first metallized film formed by iron with an electron microscope (TEM), which proves that the presence of iron at 1 X 105 nm2 Any area is an island structure. (3) The surface of the first metal film made of iron is replaced with palladium by immersing the support member on which the first metal film is formed in a gasified palladium-hydrochloric acid aqueous solution for 1 minute. Thus, a second metal film made of palladium is formed. (4) The support member having the second metal film formed thereon is immersed in an electroless nickel-phosphorus alloy plating bath similar to step (3) of Example 1 and maintained for a similar immersion time. Therefore, A third metal film is formed by electroless plating. The thickness of the formed metal film was 0.7 μm. _____ _ 22-& Zhang scale is applicable to Chinese National Standard (CNS) ^ 4 specifications (210 X 297 mm) 20 5. Description of the invention (The metal film is defect-free and has excellent mold release properties. 3. Example 3 ⑴Manufacture Similar to the support element and metal mask of Example 丨. ⑺ The metal mask is closely adhered to the surface of the release layer side of the support element. The vacuum mask is used to borrow the metal mask to use a quartz resonator. The film formation rate based on the thickness gauge was 6 A / sec. Evaporation of silver was performed together. 'The first metal film was formed on the opening of the metal mask. The first metal film formed of silver was observed with an electron microscope (TEM), and it was proved to exist Any area of the first metal film x 10W is an island structure. ^ M (3) The supporting element on which the first metal film is formed is immersed in a step (3) similar to that in Example 1. In the electroless nickel-phosphorus alloy plating bath, and maintaining a similar immersion time, a second metal film is formed by electroless plating. The thickness of the resulting metal film is 0.6 micrometers. The metal film is defect-free and has Excellent mold release. 4 · Example 4 (1) Manufacturing similar (1) The support element and the metal mask in the embodiment (1). (2) The metal mask is closely adhered to the surface of the release layer side of the support element. The metal mask is borrowed by a vacuum evaporation device to Quartz crystals were evaporated at a film-forming rate of 5 A / sec for 10 seconds to form a first metal film on the opening of the metal mask. The first metal film formed of silver was observed with a hair microscope (TEM). It proves that the first metal film exists in any region of 1 x 105 nm2 as an island squirrel. ° 21 V. Description of the invention (
由此形成由鈀製成的第二金屬膜。Thereby, a second metal film made of palladium is formed.
實施例1步驟（3)的無電鍍鎳-磷合金鍍本 L件浸潰在類似於 中’並維持與其類 似的浸潰時間，由此藉無電鍍形成第三金屬膜 由此形成的金屬膜厚度爲0.7微米。 該金屬膜無缺陷且具有優異脫模性。 5·實施例5 (1)製造類似於實施例丨之^)的支撐元件和金屬掩模。The electroless nickel-phosphorus alloy plated L-pieces of the step (3) of Example 1 were immersed in a medium-like shape and maintained a similar immersion time, thereby forming a third metal film by electroless plating to thereby form a metal film. The thickness is 0.7 microns. The metal film is defect-free and has excellent release properties. 5. · Embodiment 5 (1) A support element and a metal mask similar to those in Embodiment 丨 ^) were manufactured.
用電子顯微鏡（TEM)觀察由鈀形成的第一金屬膜，其證 明存在的第一金屬膜在1 x iMnm2的任何區域内為島嶼結 屬掩模開口上形成第一金屬膜。 (3) 將其上形成有第一金屬膜的支撐元件浸潰在氯化鈀 •鹽酸水溶液1分鐘，用鈀置換由銅製成的第一金屬膜表面 ’由此形成由ίε製成的第二金屬膜。 (4) 將其上形成有第二金屬膜的支撐元件浸潰在類似於 貫施例1步驟（3)的無電鍍鎳-磷合金鍍槽中，並維持與其類 似的浸潰時間，由此藉無電鍍形成第三金屬膜。 由此形成的金屬膜厚度爲〇·7微米。The first metal film formed of palladium was observed with an electron microscope (TEM), and it was proved that the first metal film was formed on the opening of the island-shaped mask in any region of 1 x iMnm2. (3) The support member on which the first metal film is formed is immersed in an aqueous solution of palladium chloride and hydrochloric acid for 1 minute, and the surface of the first metal film made of copper is replaced with palladium, thereby forming a second made of ε Metal film. (4) The support member having the second metal film formed thereon is immersed in an electroless nickel-phosphorus alloy plating bath similar to step (3) of Example 1 and maintained for a similar immersion time, thereby A third metal film is formed by electroless plating. The thickness of the metal film thus formed was 0.7 μm.
574416574416
該金屬膜無缺陷且具有優異脫模性。 6 ·比較例1 (1) 製造類似於實施例1之（1)的支撐元件和金屬掩模。 (2) 將上述金屬掩模緊密黏合到上述支撐元件的脫模層 一側表面上。利用真空蒸發設備藉該金屬掩模，以石英譜 振裔尽度计爲準的！人以⑶成膜速率蒸發把1⑻秒，在金屬掩 模開口處形成第一金屬膜。 用電子顯微鏡（TEM)觀察由把形成的第一金屬膜，其證 明第一金屬膜在1 χ 1〇5 nm2的任何區域内為均勻的連續膜。 (3) 浸潰在類似於實施例1步驟（3)的無電鍍鎳_磷合金鍍 槽中，並維持與其類似的浸潰時間，由此藉無電鍍形成第 二金屬膜。 然而，在該無電鍍和鍍膜後的水洗過程中，第二金屬膜 與第一金屬膜一起剝離，因此金屬膜無法良好地形成。 7·比較例2 (1) 製造類似於實施例1之（1)的支撐元件和金屬掩模。 (2) 將上述金屬掩模緊密黏合到上述支撐元件的脫模層 一側表面上。利用真空蒸發設備藉該金屬掩模，以石英諧 振器厚度計爲準的10 Α/sec的成膜速率蒸發鎳1〇〇秒，在金 屬掩模開口處形成第一金屬膜。 用電子顯微鏡（TEM)觀察由鎳形成的第一金屬膜，其證 明第一金屬膜在1 χ l〇5nm2的任何區域内為均勻的連續膜。 (3) 將其上形成有第一金屬膜的支撐元件浸潰在類似於 實施例1步驟（3)的無電鍍鎳-磷合金鍍槽中，並維持與其類 ___ - 25 _ 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)' 23The metal film is defect-free and has excellent release properties. 6 · Comparative Example 1 (1) A support member and a metal mask similar to those in (1) of Example 1 were manufactured. (2) The metal mask is tightly adhered to the release layer side surface of the support member. Use the vacuum evaporation equipment to borrow the metal mask, which is based on the quartz spectrum vibrometer. A person evaporates at a film-forming rate for 1 second, and a first metal film is formed at the opening of the metal mask. Observation of the first metal film formed by the handle with an electron microscope (TEM) confirmed that the first metal film was a uniform continuous film in any region of 1 x 105 nm2. (3) Immersion in an electroless nickel-phosphorus alloy plating bath similar to step (3) of Example 1 and maintaining a similar immersion time, thereby forming a second metal film by electroless plating. However, during the electroless plating and the water washing process after the plating, the second metal film is peeled together with the first metal film, so the metal film cannot be formed well. 7. Comparative Example 2 (1) A support member and a metal mask similar to those in (1) of Example 1 were manufactured. (2) The metal mask is tightly adhered to the release layer side surface of the support member. Using a vacuum evaporation device to borrow the metal mask, nickel was evaporated at a film formation rate of 10 A / sec based on the thickness of the quartz resonator for 100 seconds to form a first metal film at the opening of the metal mask. Observation of the first metal film formed of nickel with an electron microscope (TEM) proved that the first metal film was a uniform continuous film in any region of 1 x 105 nm2. (3) The support member having the first metal film formed thereon is immersed in an electroless nickel-phosphorus alloy plating bath similar to step (3) of Example 1 and maintained similar to that of the paper ___-25 _ Applicable to China National Standard (CNS) A4 (210 X 297 mm) '23
膜作爲内部電極 五、發明説明（ 該試驗中，利用試驗丨中實施例丨的金屬 製造多層陶瓷電容器。 藉刮刀方法在其上形成有金屬膜的支撐元件上形成厚产 7微米之含有鈦酸鋇作主要材料的陶瓷生板7。 藉重復壓接多個複合體的方法製造具有多個金屬膜和多 個陶瓷生板的粗胚疊層體，其中該各複合體係由陶瓷生= 和金屬膜疊層在一起所構成。複合體彼此壓接係藉由從支 撐元件一側施加壓力而進行。 該步驟中’金屬膜從支撐元件上的剝離性優異。 將粗胚疊層體切成預定大小，隨後在1200°C烘焙。隨後 ’形成端電極，並因此製造多層陶瓷電容器。 在不偏離後述申請專利範圍限定的本發明範圍前提下， 可以對所描述的具體例進行多種改變，且熟知本技術者也 可對其進行改變。 -26- 本紙張尺歧财國國緖準A4_2ig χ撕公赞)Film as an internal electrode V. Description of the invention (In this test, a multilayer ceramic capacitor was manufactured using the metal of Example 丨 in the test. The 7-micrometer-thick titanium titanate-containing acid was formed on the supporting member on which the metal film was formed by a doctor blade method. Barium as the main material of the ceramic green sheet 7. A method of repeatedly crimping a plurality of composite bodies to produce a rough embryo laminated body having a plurality of metal films and a plurality of ceramic green plates, wherein each composite system is composed of ceramic raw materials and metals. The films are laminated together. The composite bodies are pressure-bonded to each other by applying pressure from the support element side. In this step, the metal film has excellent peelability from the support element. The rough embryo laminate is cut into a predetermined shape. Size, and then baked at 1200 ° C. Subsequently, a terminal electrode is formed, and thus a multilayer ceramic capacitor is manufactured. Without departing from the scope of the present invention, which is limited by the scope of the patent application to be described later, various changes can be made to the specific examples described, and are well known The person skilled in the art can also change it. -26- This paper ruler is rich in money and the country is a standard A4_2ig
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001174251 | 2001-06-08 | ||
| JP2002099749A JP3656612B2 (en) | 2001-06-08 | 2002-04-02 | Metal film and manufacturing method thereof, multilayer ceramic electronic component and manufacturing method thereof |
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| Publication Number | Publication Date |
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| TW574416B true TW574416B (en) | 2004-02-01 |
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| TW91111046A TW574416B (en) | 2001-06-08 | 2002-05-24 | Metal film and manufacturing method therefor, and laminated ceramic electronic component and manufacturing method therefor |
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| Country | Link |
|---|---|
| US (1) | US6967163B2 (en) |
| JP (1) | JP3656612B2 (en) |
| KR (1) | KR100486759B1 (en) |
| CN (1) | CN100463084C (en) |
| DE (1) | DE10225680B4 (en) |
| GB (2) | GB0212286D0 (en) |
| TW (1) | TW574416B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI408711B (en) * | 2007-10-19 | 2013-09-11 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
| TWI419187B (en) * | 2008-01-11 | 2013-12-11 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
| TWI420550B (en) * | 2007-10-19 | 2013-12-21 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
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| US20060228534A1 (en) * | 2005-04-08 | 2006-10-12 | Battelle Memorial Institute | Method for reduction of islanding in metal layers formed on dielectric materials |
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| JP5737878B2 (en) * | 2010-08-04 | 2015-06-17 | 上村工業株式会社 | Electroless plating method and LED mounting substrate |
| US20120058362A1 (en) * | 2010-09-08 | 2012-03-08 | Infineon Technologies Ag | Method for depositing metal on a substrate; metal structure and method for plating a metal on a substrate |
| CN102560370B (en) * | 2010-12-29 | 2014-07-16 | 鸿富锦精密工业（深圳）有限公司 | Covered member and manufacturing method thereof |
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| CN102758187B (en) * | 2011-04-27 | 2015-05-20 | 鸿富锦精密工业（深圳）有限公司 | Surface coating method for iron-based alloy and coated part prepared by surface coating method |
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2002
- 2002-04-02 JP JP2002099749A patent/JP3656612B2/en not_active Expired - Fee Related
- 2002-05-24 TW TW91111046A patent/TW574416B/en not_active IP Right Cessation
- 2002-05-28 GB GBGB0212286.9A patent/GB0212286D0/en not_active Ceased
- 2002-06-07 GB GB0213112A patent/GB2377227B/en not_active Expired - Fee Related
- 2002-06-08 KR KR10-2002-0032153A patent/KR100486759B1/en not_active IP Right Cessation
- 2002-06-10 CN CNB021227527A patent/CN100463084C/en not_active Expired - Fee Related
- 2002-06-10 US US10/164,564 patent/US6967163B2/en not_active Expired - Fee Related
- 2002-06-10 DE DE10225680.2A patent/DE10225680B4/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI408711B (en) * | 2007-10-19 | 2013-09-11 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
| TWI420550B (en) * | 2007-10-19 | 2013-12-21 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
| TWI419187B (en) * | 2008-01-11 | 2013-12-11 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020093640A (en) | 2002-12-16 |
| GB2377227A (en) | 2003-01-08 |
| CN100463084C (en) | 2009-02-18 |
| GB2377227B (en) | 2004-01-14 |
| DE10225680B4 (en) | 2014-07-31 |
| GB0212286D0 (en) | 2002-07-10 |
| CN1391242A (en) | 2003-01-15 |
| JP2003055775A (en) | 2003-02-26 |
| DE10225680A1 (en) | 2003-08-21 |
| KR100486759B1 (en) | 2005-05-03 |
| US20030022492A1 (en) | 2003-01-30 |
| US6967163B2 (en) | 2005-11-22 |
| JP3656612B2 (en) | 2005-06-08 |
| GB0213112D0 (en) | 2002-07-17 |
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